CN103524554A - Method for recycling glyphosate from glyphosate wastewater - Google Patents
Method for recycling glyphosate from glyphosate wastewater Download PDFInfo
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- CN103524554A CN103524554A CN201310493816.8A CN201310493816A CN103524554A CN 103524554 A CN103524554 A CN 103524554A CN 201310493816 A CN201310493816 A CN 201310493816A CN 103524554 A CN103524554 A CN 103524554A
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Abstract
The invention discloses a method for recycling glyphosate from glyphosate wastewater, which comprises the following steps: pretreating glyphosate wastewater to remove suspended substances and large-granule impurities, and regulating the pH value to 3.0-3.5; carrying out membrane separation preconcentration, dividing the glyphosate mother solution into a concentrated solution and a diluted solution, sending the concentrated solution into a tertiary membrane concentration system, and concentrating until the mass percent of glyphosate in the concentrated solution is 5-10 wt%, sending the diluted solution into a quarternary membrane recovery system, merging the diluted solutions, and sending into a secondary membrane system to carry out cyclic concentration; sending the concentrated glyphosate solution into an MVR (mechanical vapor recompression) low-temperature evaporation concentration system, carrying out concentration treatment at 40-50 DEG C for 1.5-2 hours until the mass percent is 20-30%, and crystallizing to obtain the glyphosate solid of which the mass percent is greater than 95%. After the membrane separation preconcentration and MVR low-temperature evaporation concentration, the recrystallization is performed to recover the glyphosate, so that the glyphosate recovery rate of the whole glyphosate wastewater treatment system can reach higher than 90%.
Description
Technical field
The present invention relates to method of wastewater treatment, refer to particularly a kind of method of recycling glyphosate from glyphosate waste water.
Background technology
Glyphosate chemical name is N-(phosphine carboxymerhyl) glycine, it is the natural disposition organophosphorus herbicide that goes out of a kind of efficient, low toxicity, wide spectrum, there is good interior suction, conductive performance, very effective to preventing and kill off of multiple dark root malignant weed, in current agriculture production, having obtained using widely, is the kind of current weedicide output maximum.
At present, the most of glyphosate production of China is to take glycine, paraformaldehyde, dimethylphosphite by condensation, hydrolysis, crystallization, filtration, to make the glyphosate products that massfraction is 95% as raw material.And meeting produces a large amount of contaminative waste water in the process of application the method production glyphosate, due to the sodium-chlor that contains high density in this waste water, and contain a certain amount of glyphosate and byproduct of reaction, CODcr value is high, if directly discharge meeting causes severe contamination to environment, this waste water be treated as the important subject in industry.
Because glyphosate production wastewater contains a large amount of sodium-chlor and a certain amount of organophosphorus and byproduct of reaction, on processing, there is following difficult point: if 1 directly waste water is carried out to calcification and remove organophosphorus, the throw out producing contains a large amount of organophosphoruss, and environment is still to a kind of Hazardous wastes; If 2 adopt membrane treatment process to remove organophosphorus, film easily stops up, and often will change film, and system operation cost is too high, and enterprise is difficult to bear; If 3 directly carry out biochemical treatment to waste water, because of the too high ecotope that can destroy microorganism existence in biochemical system of waste water saltiness, finally do not reach expection treatment effect; If 4 adopt common vaporizer to concentrate desalination, its shortcoming is to adopt continuously salt, the desalination that must turn off steam after condensing crystal, and discontinuous is produced and is caused steam consumption large, and processing efficiency is low.
The massfraction that produces in process of production glyphosate in a large amount of waste water is only 1% left and right, traditional treatment method is by membrane concentration to 7% left and right by this waste water, because concentration is lower and impurity effect, be difficult to crystallization and get powder, can only prepare 10% aqua by the former powder of interpolation glyphosate and sell.On December 31st, 2009 rises, and it is 10% gyphosate solution and massfraction lower than other all kinds of formulation kinds that contain glyphosate of 30% that country has prohibited quality of production mark.Therefore, the traditional treatment method of glyphosate waste water has been difficult to continue application, in the urgent need to improving.
Summary of the invention
Object of the present invention will overcome the existing deficiency of prior art exactly, and a kind of method of recycling glyphosate from glyphosate waste water is provided.
For achieving the above object, the present invention recycles the method for glyphosate from glyphosate waste water, comprises the following steps:
1), first by glyphosate waste water pre-treatment, remove suspended substance and oarse-grained impurity wherein, and regulate PH to 3.0～3.5;
2) pretreated glyphosate mother solution is carried out to membrane sepn pre-concentration, glyphosate mother solution is divided into dope and light liquid two portions, dope enters three grades of membrane concentration systems, after concentration, in dope, glyphosate massfraction is 5～10%, light liquid enters level Four film recovery system, light liquid merging is entered to secondary film system again and circulate concentrated;
3) the glyphosate dope after concentrated is entered to MVR low-temperature evaporation concentration systems, concentration 1.5～2h at 40～50 ℃, being further concentrated into massfraction is 20～30%, then crystallization obtains the glyphosate that massfraction is greater than 95%.
In step 1), the pretreatment system that glyphosate waste water pre-treatment adopts mainly forms easy, efficient, an economic filtering system by filter core, filtrate, strainer three parts, waste water enters strainer by entrance, after filter, flow out, can guarantee that pretreated glyphosate mother solution reaches the requirement that enters rear level system.
Step 2) in, by the light liquid after two-stage concentration, can enter Waste Water Treatment, carry out ammonification and remove formaldehyde, then enter biochemical treatment system, treated qualified rear discharge.
When step 3) is passed through MVR low-temperature evaporation concentration systems, behind first pre-heating temperature elevation to 40～50 ℃, enter vaporizer circulation tube, after heating up, interchanger enters evaporator room evaporation, temperature of charge is 40～50 ℃, secondary steam temperature is 40～45 ℃, solution, through dropping to base of evaporator, then pumps into interchanger and heats up under the attraction of recycle pump, enters circulation next time.
Because containing formaldehyde in glyphosate waste water, can generate N-methyl glyphosate with glyphosate reaction at a certain temperature, in order effectively to control the generation of this side reaction, while energy efficient, vaporization temperature is 40～50 ℃ of the bests.
System continuously feeding discharging need to improve its pressure and temperature of saturation with the secondary steam of cooling water condensation originally by vaporizer after compressor compression, increases enthalpy, then sends into vaporizer well heater and heat feed liquid as thermal source.The latent heat of secondary steam is fully utilized, and glyphosate waste water content will further be concentrated into 20～30% by 5～10%, and processing efficiency is high.
The light liquid that glyphosate mother solution is discharged after concentration enters Waste Water Treatment, the materials such as formaldehyde is removed by ammonification, then enter biochemical treatment system processing qualified discharge, environmentally safe.
Beneficial effect of the present invention is: the present invention is concentrated by membrane sepn pre-concentration and MVR low-temperature evaporation, and recrystallize reclaims glyphosate, and the glyphosate rate of recovery of whole glyphosate waste water treatment system can reach more than 90%.
Embodiment
In order to explain better the present invention, below in conjunction with specific embodiment, the present invention is described in further detail.
Example 1
Glyphosate waste water 7800L, wherein glyphosate massfraction is 1.1%, glyphosate waste water is entered the strainer of pretreatment system by entrance, after filter, flow out, remove by filter a small amount of large particulate matter and suspended substance, and pass into ammonia to pH value 3.0, enter film separating system.
First be secondary membrane concentration, glyphosate mother solution is divided into dope and light liquid two portions, in light liquid, the massfraction of glyphosate is 0.05%, and in dope, the massfraction of glyphosate is 3.75%; Dope enters three grades of membrane concentration systems, and after concentration, the massfraction of dope is 6.34%, and light liquid enters level Four film recovery system, light liquid merging is entered to secondary film system again and circulate concentrated.By the light liquid after two-stage concentration, can enter Waste Water Treatment, carry out ammonification and remove formaldehyde, then enter biochemical treatment system, treated qualified rear discharge.
Massfraction is that the concentrated dope of 6.34% glyphosate enters MVR low-temperature evaporation concentration systems, first after pre-heating temperature elevation to 40 ℃, enter vaporizer circulation tube, after heating up, interchanger enters evaporator room evaporation, temperature of charge is 40 ℃, secondary steam temperature is 40 ℃, solution, through dropping to base of evaporator, then pumps into interchanger and heats up under the attraction of recycle pump, enters circulation next time.After concentration 2h, quality of material mark reaches 22%, direct crystallization, and obtaining glyphosate massfraction is 96.70%, and weight is 81.29kg, and the rate of recovery is 91.63%.
Example 2
Glyphosate waste water 8050L, wherein glyphosate massfraction is 0.98%, glyphosate waste water is entered the strainer of pretreatment system by entrance, after filter, flow out, remove by filter a small amount of large particulate matter and suspended substance, and pass into ammonia to pH value 3.5, enter film separating system.
First be secondary membrane concentration, glyphosate mother solution is divided into dope and light liquid two portions, in light liquid, glyphosate massfraction is 0.04%, and in dope, glyphosate massfraction is 3.95%; Dope enters three grades of membrane concentration systems, and after concentration, dope massfraction is 7.01%, and light liquid enters level Four film recovery system, light liquid merging is entered to secondary film system again and circulate concentrated.By the light liquid after two-stage concentration, can enter Waste Water Treatment, carry out ammonification and remove formaldehyde, then enter biochemical treatment system, treated qualified rear discharge.
Massfraction is that 7.01% glyphosate mother solution waste water enters MVR low-temperature evaporation concentration systems, first after pre-heating temperature elevation to 50 ℃, enter vaporizer circulation tube, after heating up, interchanger enters evaporator room evaporation, temperature of charge is 50 ℃, secondary steam temperature is 45 ℃, solution, through dropping to base of evaporator, then pumps into interchanger and heats up under the attraction of recycle pump, enters circulation next time.After concentration 1.5h, quality of material mark reaches 20.5%, direct crystallization, and obtaining glyphosate massfraction is 97.95%, and weight is 74.34kg, and the rate of recovery is 92.30%
The enforcement object of above-mentioned example is further to explain technical characterstic of the present invention and practical value, is the explanation to General Principle of the present invention, plays the effect that helps technician to understand and apply.The present invention is not limited in described concrete detailed rules for the implementation and the scheme of above-mentioned example, within the improvement that the present invention has been done and modification all will be included in protection scope of the present invention.
Claims (3)
1. from glyphosate waste water, recycle a method for glyphosate, it is characterized in that, comprise the following steps:
1), first by glyphosate waste water pre-treatment, remove suspended substance and oarse-grained impurity wherein, and regulate PH to 3.0～3.5;
2) pretreated glyphosate mother solution is carried out to membrane sepn pre-concentration, glyphosate mother solution is divided into dope and light liquid two portions, dope enters three grades of membrane concentration systems, after concentration, in dope, glyphosate massfraction is 5～10%, light liquid enters level Four film recovery system, light liquid merging is entered to secondary film system again and circulate concentrated;
3) the glyphosate dope after concentrated is entered to MVR low-temperature evaporation concentration systems, concentration 1.5～2h at 40～50 ℃, being further concentrated into massfraction is 20～30%, then crystallization obtains the glyphosate that massfraction is greater than 95%.
2. according to the method for recycling glyphosate from glyphosate waste water described in claims 1, it is characterized in that: step 2) in, by the light liquid after two-stage concentration, can enter Waste Water Treatment, carry out ammonification and remove formaldehyde, then enter biochemical treatment system, treated qualified rear discharge.
3. according to the method for recycling glyphosate from glyphosate waste water described in claims 1, it is characterized in that: when step 3) is passed through MVR low-temperature evaporation concentration systems, behind first pre-heating temperature elevation to 40～50, ℃ enter vaporizer circulation tube, after heating up, interchanger enters evaporator room evaporation, temperature of charge is 40～50 ℃, and secondary steam temperature is 40～45 ℃, and solution is through dropping to base of evaporator, then under the attraction of recycle pump, pump into interchanger and heat up, enter circulation next time.
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| CN201310493816.8A CN103524554B (en) | 2013-10-21 | 2013-10-21 | The method of glyphosate is recycled from glyphosate waste water |
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| CN201310493816.8A CN103524554B (en) | 2013-10-21 | 2013-10-21 | The method of glyphosate is recycled from glyphosate waste water |
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| CN103524554A true CN103524554A (en) | 2014-01-22 |
| CN103524554B CN103524554B (en) | 2016-03-16 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110921996A (en) * | 2019-12-18 | 2020-03-27 | 水清华(天津)环保科技有限公司 | Glyphosate wastewater treatment method |
| CN113827992A (en) * | 2021-10-20 | 2021-12-24 | 镇江江南化工有限公司 | Method for recycling water separated from alkali mother liquor rectification tower top fraction in glyphosate production process |
| CN114212940A (en) * | 2021-12-13 | 2022-03-22 | 浙江新安化工集团股份有限公司 | Glyphosate production sewage treatment system and method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792216A (en) * | 2010-02-09 | 2010-08-04 | 丁国良 | Resource recycling method of glyphosate mother liquor |
| CN101967161A (en) * | 2010-04-22 | 2011-02-09 | 浙江新安化工集团股份有限公司 | Comprehensive treatment method for glyphosate mother liquid |
| CN103342398A (en) * | 2013-07-17 | 2013-10-09 | 山东潍坊润丰化工有限公司 | Method for recovering high-purity organic salt from phosphorous-containing industrial wastewater |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792216A (en) * | 2010-02-09 | 2010-08-04 | 丁国良 | Resource recycling method of glyphosate mother liquor |
| CN101967161A (en) * | 2010-04-22 | 2011-02-09 | 浙江新安化工集团股份有限公司 | Comprehensive treatment method for glyphosate mother liquid |
| CN103342398A (en) * | 2013-07-17 | 2013-10-09 | 山东潍坊润丰化工有限公司 | Method for recovering high-purity organic salt from phosphorous-containing industrial wastewater |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110921996A (en) * | 2019-12-18 | 2020-03-27 | 水清华(天津)环保科技有限公司 | Glyphosate wastewater treatment method |
| CN113827992A (en) * | 2021-10-20 | 2021-12-24 | 镇江江南化工有限公司 | Method for recycling water separated from alkali mother liquor rectification tower top fraction in glyphosate production process |
| CN114212940A (en) * | 2021-12-13 | 2022-03-22 | 浙江新安化工集团股份有限公司 | Glyphosate production sewage treatment system and method |
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